Patent GB-314909-A (GB)
Title: Improvements in the manufacture of ureas and thioureas of the naphthalene series
IPC: C07C309/51
Filed: 1928-02-01
Abstract: 314,909. Dyson, G. M., and Renshaw, A. Feb. 1, 1928. Samples furnished. Urea and thiourea derivatives. - Ureas and thioureas containing two aryl carboxylic acid groups or one aryl and one heterocyclyl carboxylic acid group are converted into the acid chlorides by treatment with thionyl chloride, phosphorus chlorides, &c. Similar compounds are also obtained by treating aryl isocyanates or isothiocyanates containing carboxylic acid groups with thionyl chloride, phosphorus chlorides, &c., combining the resulting carbimide or thiocarbimide aryl acidyl halides with aminoaryl or aminoheterocyclyl carboxylic acids, and finally treating with thionyl chloride. The products of either process are converted into symmetrical and unsymmetrical urea and thiourea derivatives by treatment with 1-aminonaphthalene sulphonic acids or with the products obtained by reducing the nitro compounds obtained by the action of 1-aminonaphthalene sulphonic acids or of aminoacenaphthene sulphonic acid on chlorides of nitroaryl fatty acids, nitroaroyl chlorides, nitroaryl olefinic carboxylic acid chlorides and nitroaryl sulphochlorides. Of the 1-aminonaphtihalene sulphonic acids, the following are mentioned :- 1 :8 - aminonaphthol-3 : 6 - disulphonic acid, 1- naphthylamine-4 : 8-disulphonic acid, 1-naphthylamine - 4 : 6 : 8 - trisulphonic acid, 1 - amino-5- naphthol-7-sulphonic acid, and chloro-, bromo, iodo-, and alkoxy--1-naphthylamine sulphonic acids. Specified aminoacenaphthene sulphonic acids are 4-aminoacenaphthene-3- or 5-sulphonic acid, 4-aminoacenaphthene-3: 5-disulphonic acid and 4-aminoacenaphthene trisulphonic acids. As examples of substituents for the production of substituted 1-naphthylamine sulphonic acids are mentioned:-2-, 3. or 4-nitrocinnamyl chloride ; 1-nitronaphthalene-5-sulphochloride, 1: 5-nitronaphthoyl chloride, 2- or 4-nitrophenylacetyl chloride, nitrobenzoyl chlorides, nitroanisoyl chlorides, nitrotoluyl chlorides, nitrobenzene sulphochlorides, and chloro-, bromo- or iodo-nitrobenzoyl chlorides. Urea or thiourea dicarboxylic acids specified are s-diphenylurea (or thiourea)-3 : 3<1>-dicarboxylic acid, s-benzthiazolylphenylurea-3 : 5<1>dicarboxylic acid, as-diphenylurea-3 3<1>-dicarboxylic acid, s-4-quinolylphenylurea-3 : 6<1>-dicarboxylic acid, and s-a-2-methoxyphenyl - # - 4 - nitrophenylurea - 3 : 3<1>-dicarboxylic acid. The final products are useful as therapeutic agents and as intermediates for dyestuff production. According to the examples, (1) diphenylurea-3 : 3<1>-dicarboxylic acid is prepared by interaction of m-aminobenzoic acid and phosgene, and is converted into its acid chloride by treatment with thionyl chloride; the acid chloride is then brought into reaction with m-aminotoluyl-1- naphthylamine-4 : 6 : 8-trisulphonic acid; (2) maminobenzoic acid is treated with thiophosgene and the resulting 3-carboxyphenylthiocarbimide converted into its acid chloride by means of thionyl chloride; the product is then treated in succession with m-aminobenzoic acid, thionyl chloride, and m-amino-p-toluyl-1-naphthylamine- 4: 6 : 8-trisulphonic acid. The Provisional Specification also contains n diagrammatic representation of the interaction of 3-carboxyphenylthiocarbimide with 1-aminobenzthiazole-5-carboxylic acid, and treatment of the product first with thionyl chloride and then with m-aminobenzoyl- 1-naphthylamine-4 : 6 : 8-trisulphonic acid. Halogen-1-naphthylamine sulphonic acids are prepared by halogenating 1-naphthylamine sulphonic acids, or by halogenating the corresponding acetyl compounds and hydrolysing. 4 - Aminoacenaphthene trisulphonic acids are obtained by sulphonation of 4-aminoacenaphthene- 5-sulphonic acid with oleum, or of 4-nitroacenaphthene-5-sulphonic acid and reduction of the nitro group. as - Diphenylurea - 3 : 3<1> - dicarboxylic acid is formed when diphenylamine-3 : 3'-dicarboxylic acid is treated with phosgene and the product boiled with aqueous ammonia. s - Benzthiazolylphenylurea-3 5<1>-dicarboxylic acid is produced when 1-aminobenzthiazole-5- carboxylic acid is heated with 3-carboxyphenyl isocyanate. s-4-Quinolylphenylurea-3 6'-dicarboxylic acid results from the interaction of 4-aminoquinoline- 6-carboxylic acid and 3-carboxyphenyl isocyanate. s - a-Methoxyphenyl-#-4-nitrophenylurea-3 : 3<1>- dicarboxylic acid is prepared by heating 2-nitro- 5 aminobenzoic acid with 2-methoxy-3-carboxyphenyl isocyanate.